CN101679747B - Thermosetting silicone rubber composition - Google Patents
Thermosetting silicone rubber composition Download PDFInfo
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- CN101679747B CN101679747B CN2007800482515A CN200780048251A CN101679747B CN 101679747 B CN101679747 B CN 101679747B CN 2007800482515 A CN2007800482515 A CN 2007800482515A CN 200780048251 A CN200780048251 A CN 200780048251A CN 101679747 B CN101679747 B CN 101679747B
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract
A thermosetting silicone rubber composition that contains a cerium oxide powder in an amount of 0.001 1 to 10 mass % and that is characterized by total transmittance of light equal to or greater than 90% according to JIS K7105 when the light is passed through a 1 mm-thick layer of an alkenyl-containing dimethylpolysiloxane gumwith 0.1 mass % of said cerium oxide powder dispersed in the gum.
Description
Technical field
The present invention relates to and specific ceria oxide powder blended heat-curable silicone rubber compositions.
Background technology
The known ceria oxide powder that in rubber composition, adds is as compressive set improving agent and heat-resistant agent (S52-14654 reaches and discloses S60-173050 referring to for example Japanese Unexamined Patent Application open (below be called " disclose ")).Yet, when being exposed to temperature to the uncured rubber composition of having introduced ceria oxide powder above 70 ℃, because the hyperergy of ceria oxide powder, rubber composition that this is uncured or acquisition HV, or become partial cross-linked.For must with the production of the rubber composition of ceria oxide powder combination in avoid above problem, with the mixture of said composition and ceria oxide powder or directly in mediating mixing machine, be cooled to enough degree, or cooling off flowing out from mediating mixing machine.This scheme need be used specific mixing equipment and can not shorten production technique.And the cured product that is obtained by the conventional rubber composition with the ceria oxide powder combination is opaque, so it has limited usage range.
Open 2000-212444 discloses ceria oxide powder has been introduced the rubber composition of pH in the aqueous dispersions of pre-determined range.Yet under uncured state, the thermostability of this rubber composition is not enough, and for obtaining that compressive set improves and at the cured body that is higher than heat-stable compsn under 200 ℃ the temperature, must adding cerium oxide in large quantities.
Summary of the invention
The purpose of this invention is to provide the heat-curable silicone rubber compositions that during preparation has before excellent thermostability and after curing, form Zylox with high heat resistance characteristic with curing.
Through being provided, following heat-curable silicone rubber compositions realizes above-mentioned purpose; This heat-curable silicone rubber compositions contains ceria oxide powder with the amount of 0.001～10 quality % and it is characterized in that when the said ceria oxide powder of light through 0.1 quality % is scattered in thick this of 1mm in the dimethyl polysiloxane rubber that contains alkenyl and contains the dimethyl polysiloxane rubber [layer] of alkenyl, is equal to or greater than 90% according to the total light transmittance of JIS K7105.
Advise that aforementioned heat-curable silicone rubber compositions comprises: 100 mass parts contain the diorganopolysiloxanecompositions (A) of alkenyl; 5～150 mass parts reinforcing fillers (B); Solidifying agent (C) (to be enough to solidify the amount of aforementioned heat-curable silicone rubber compositions); And ceria oxide powder (D); When the amount with 0.1 quality % is distributed to ceria oxide powder (D) in the dimethyl polysiloxane rubber that contains alkenyl; When layer of light, 90% the total light transmittance (content of component (D) in compsn is 0.001～10 quality %) of being equal to or greater than according to JIS K7105 is provided through the thick said dimethyl polysiloxane rubber of 1mm.Advise that also this solidifying agent comprises organo-peroxide.
Advise that aforesaid ceria oxide powder comprises the surface treated ceria oxide powder through the sol-gel method preparation.
Because during the preparation compsn, ceria oxide powder can mix under relatively-high temperature with heat-curable silicone rubber compositions of the present invention, this make to shorten PT and raising compsn and becomes possibility during manufacture and in the thermostability of its uncured state.Thermoset composition of the present invention make to form the compressive set that demonstrates excellent thermotolerance, reduction and be exposed to surpass 200 ℃ temperature after physicals for example the moulding silicone rubber products that reduces of the infringement of tensile strength become possibility.And, heat-curable silicone rubber compositions of the present invention be characterised in that said composition make to form the compressive set that demonstrates reduction, be exposed to surpass 200 ℃ temperature after physicals for example the moulding silicone rubber products that reduces of the infringement of tensile strength and transparent or semitransparent thermostabile bodies become possibility.Ceria oxide powder can reduce the lower heat-curable silicone rubber compositions of cerium oxide add-on cured product compressive set and can obtain the product of transparent or semitransparent form; This ceria oxide powder is characterised in that; When light is dispersed in thick this of 1mm in the dimethyl polysiloxane rubber that contains alkenyl when containing the layer of dimethyl polysiloxane rubber of alkenyl through the said ceria oxide powder of 0.1 quality %, be equal to or greater than 90% according to the total light transmittance of JIS K7105.
Embodiment
The ceria oxide powder that uses among the present invention is characterised in that; When light contains the layer of dimethyl polysiloxane rubber of alkenyl through thick this of the 1mm in the dimethyl polysiloxane rubber that the 0.1wt.% ceria oxide powder is dispersed in contain alkenyl, provide to be equal to or greater than 90% total light transmittance according to JIS K7105.This ceria oxide powder is the powder compounds with following formula: CeO
a(wherein " a " is 0.2～2.1 number).Above-mentioned powder can also comprise the hydrate of conduct and small amount of crystalline water bonded above-claimed cpd.
For the processing property of improvement is provided; The dimethyl polysiloxane rubber that contains alkenyl that contains the dispersive ceria oxide powder can preferably have in 200000～1000000 scopes what pass through GPC (GPC) mensuration is the number-average molecular weight of benchmark with the PS, more preferably in 300000～700000 scopes.The dimethyl polysiloxane unit constitutes the main ingredient of the dimethyl polysiloxane rubber that contains alkenyl, and alkenyl plays crosslinked group.Alkenyl can be represented by vinyl, allyl group or hexenyl.Be preferably vinyl.In order to improve the handlability after the compsn that is dispersed with cerium oxide solidifies, the content of suggestion alkenyl is 0.03～0.10 quality %.
Method for being used for ceria oxide powder is dispersed in the dimethyl polysiloxane rubber that contains alkenyl has no particular limits.For example, this can adopt two rollers or three roller mixing rolls to accomplish.In order in measuring complete transmittance, constant thickness to be provided, suggestion adopts organo-peroxide curing to contain the dimethyl polysiloxane rubber of alkenyl and the mixture of ceria oxide powder.For this reason, can use the general conventional organo-peroxide that is used as the solidifying agent class of heat-curable silicone rubber compositions.Specific examples is following: Lucidol, t-butylperoxyl benzoate, peroxo-o-methyl-benzene formyl, peroxo-are to toluyl, di-t-butyl peroxide, Di Cumyl Peroxide 99,1; Two (t-butyl peroxy) 3,3 of 1-, 5-trimethyl-cyclohexane, 2; 5-dimethyl--2; 5-two (t-butyl peroxy) hexane and 2,5-dimethyl--2,5-two (t-butyl peroxy) hexin.These compounds can be separately or are used with two kinds or more kinds of combinations.Usually, based on the dimethyl polysiloxane rubber that contains alkenyl of per 100 mass parts, amount that can 0.1～2 mass parts is added organo-peroxide.
The ceria oxide powder that can obtain using among the present invention through any following ordinary method: through mechanical disintegration by be equal to or greater than 500 ℃ roasting temperature cerous carbonate or similarly the product that obtains of cerium oxide precursor prepare ceria oxide powder; Through mechanical disintegration or with acid to the cerium oxide precursor for example the reaction product between cerous carbonate and the oxygenant separate flocculation and prepare ceria oxide powder; Through cause cerous nitrate, ceric ammonium nitrate or similarly cerium salt the aqueous solution and an alkali metal salt for example the reaction between sodium salt, the ammonia etc. prepare ceria oxide powder, obtain the cerium oxide colloidal gel through sol-gel method thus; Perhaps the solution through the cerium precursor that will be obtained by the aqueous solution of cerous acetate, Cerium II Chloride etc. sprays in the flame, thereby carries out preparing ceria oxide powder from the thermolysis of gas phase.From keeping low-crystallinity and preventing the viewpoint that particle reassociates; The most preferably method of roasting oxidation cerium precursor, the method that makes cerium oxide precursor and oxidant reaction and sol-gel method; Especially; When cerium oxide through sol-gel method (referring to open H01-206435, open H04-300644 and open H09-142840) when obtaining, this makes the compressive set with the cured product of less add-on reduction heat-curable silicone rubber compositions of cerium oxide become possibility.Can in hammer mill, jet mill etc., pass through dry ground, or in wet ball mill, carry out mechanical disintegration through wet pulverization.Preferred wet pulverization method is because it promotes the coarse grained product of removing and obtain fine powder form.
The ceria oxide powder usable surface promoting agent that uses among the present invention carries out surface treatment.Can with the wet pulverization of ceria oxide powder simultaneously or during solation, carry out surface treatment operations.Can expect that the surface treatment of ceria oxide powder has the cerium oxide particle of preventing and reassociates and improve this powder dispersive effect in organopolysiloxane.Tensio-active agent for being fit to above-mentioned processing has no particular limits, and this can be conventional tensio-active agent, for example cats product, AS, nonionogenic tenside, fluorine class tensio-active agent etc.Also can ortho-phosphoric acid, condensed phosphoric acid and/or these sour an alkali metal salts or ammonia salt be used to handle ceria oxide powder.
The diameter of the primary granule of the ceria oxide powder that suggestion is used among the present invention is 1～100nm, preferred 1～30nm, and such particulate mean diameter is 10～1000nm, preferred 10～200nm.In addition, in order to improve through solidifying the thermotolerance of the Zylox that Thermocurable silicone rubber composition of the present invention obtains and be intended under the high temperature using, the percent crystallinity of suggestion ceria oxide powder is in 10～75% scope, and is and preferred in 10～50% scope.In order to improve through solidifying the thermotolerance of the Zylox that Thermocurable silicone rubber composition of the present invention obtains and be intended under the high temperature using, the BET specific surface area of suggestion ceria oxide powder is at 30m
2/ g～300m
2In the scope of/g, preferably at 50m
2/ g～300m
2In the scope of/g, and most preferably at 100m
2/ g～250m
2In the scope of/g.
Advise the above-mentioned specific content of cerium oxide compsn in heat-curable silicone rubber compositions in the scope of 0.001～10 quality %, preferred 0.001～2 quality %, and 0.005～1 quality % most preferably.Have no particular limits for solidified mechanism, and said composition can comprise conventional organo-peroxide solidified nature or hydrosilylation reactions solidified nature heat-curable silicone rubber compositions.Usually, such compsn can comprise: 100 mass parts contain the diorganopolysiloxanecompositions (A) of alkenyl; The reinforcing filler of 5～150 mass parts (B); Solidifying agent (C) (to be enough to solidify the amount of above-mentioned heat-curable silicone rubber compositions); And ceria oxide powder (D); When it is dispersed in the dimethyl polysiloxane rubber that contains alkenyl with the amount of 0.1 quality %; When layer of light, 90% the total light transmittance (content of component (D) in compsn is 0.001～10 quality %) of being equal to, or greater than according to JIS K7105 is provided through the thick said dimethyl polysiloxane rubber of 1mm.
Diorganopolysiloxanecompositions (A) is the main ingredient of heat-curable silicone rubber compositions.Preferably, this component can contain at least two and silicon bonded alkenyl in a part.Such alkenyl can be represented by vinyl, allyl group, propenyl or similar group.Organic group beyond the alkenyl can be illustrated as methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, decyl, dodecyl or similar alkyl; Phenyl, tolyl or similar aryl; β-styroyl or similar aralkyl; 3,3,3-trifluoro propyl, 3-chloropropyl or similar haloalkyl.Can small amount of hydroxyl groups be bonded to molecular end.Component (A) can have line style, ring-type or the netted molecular structure of line style, part branching, and perhaps this diorganopolysiloxanecompositions can have the above-mentioned molecular structure of two kinds or more kinds of combinations.Diorganopolysiloxanecompositions (A) can have the viscosity that changes to the high viscosity rubber from low viscosity liquid; But in order to obtain the cured product of rubber-like elastic body form; The viscosity of suggestion component (A) under 25 ℃ surpasses 100mPas; More preferably, component (A) is the form of the rubber of molecular-weight average in 200000 to 700000 scopes of benchmark with the PS for what measure through GPC (GPC).
Reinforcing filler (B) is to be used for give the component of excellent physical strength through the crosslinked Zylox that obtains with curing heat-curable silicone rubber compositions of the present invention.This reinforcing filler can be illustrated as fumed silica or similar dry method silicon-dioxide, precipitated silica or similar wet method silicon-dioxide.Silicon-dioxide can be to have carried out the fine powder form that hydrophobic surface is handled with organosilane, six organic disilazanes, diorganopolysiloxanecompositions, two organic cyclopolysiloxanes or similar silicoorganic compound.Preferably, this component can have diameter and the 50～400m that is no more than 50 μ m
2/ g, and preferred 100～400m
2The particle of the specific surface area of/g.Amount that can per 100 mass parts components (A), 5～150 mass parts adds this component.If content is lower than the lower limit of suggestion, solidifies the cured body that heat-curable silicone rubber compositions of the present invention obtains and to have insufficient physical strength.On the other hand, if content surpasses this range limit of suggestion, will be difficult to this component is mixed with component (A).
Solidifying agent (C) is to be used for when heating heat-curable silicone rubber compositions of the present invention, making its crosslinked and solidified component.This component can comprise organo-peroxide or with as the organic hydrogen polysiloxanes bonded hydrosilylation catalysts of linking agent.
Organo-peroxide can comprise the compound that routinizes of this type.But the preferred following compound of organo-peroxide illustration: 1, two (t-butyl peroxy) 3,3 of 1-, 5-trimethyl-cyclohexane, 2,5-dimethyl--2,5-two (t-butyl peroxy) hexane or 2,5-dimethyl--2,5-two (t-butyl peroxy) hexin.Usually, amount that can per 100 mass parts components (A), 0.1～5 mass parts is added organo-peroxide.
When component (A) is when having the diorganopolysiloxanecompositions of two or more alkenyls in a part, component (C) can comprise hydrosilylation catalysts and as the organic hydrogen polysiloxanes of the linking agent that uses together.Hydrosilylation catalysts can comprise conventional hydrosilylation catalysts, for example the complex compound of the alcoholic solution of Platinic chloride, Platinic chloride or Platinic chloride and alkene, vinylsiloxane or acetylide, platinum black, the platinum on solid carrier surface or similar catalyzer based on platinum; Four (triphenylphosphines) close palladium or similar catalyzer based on palladium; Or chloro-three (triphenylphosphine) rhodium or similar catalyzer based on rhodium.Be preferably based on the catalyzer of platinum.In catalytic metal element, can per 10
6Mass parts component (A) and total amount (B) are used the hydrosilylation catalysts of the amount of 0.1～500 mass parts, preferred 1～50 mass parts.If the amount with less than 0.1 weight part is used hydrosilylation catalysts, curing can't be carried out fully, and will be if add with the amount that surpasses 500 mass parts, unreasonable economically.
Organic hydrogen polysiloxanes is in the component that causes the addition reaction between organic hydrogen polysiloxanes and silicon bonded hydrogen atom and component (A) and the silicon bonded alkenyl in the presence of the above-mentioned hydrosilylation catalysts.Organic hydrogen polysiloxanes can contain at least two and silicon bonded hydrogen atom in a part.With the organic group beyond the silicon bonded hydrogen atom can give an example methyl, ethyl, propyl group or similar alkyl; Phenyl, tolyl or similar aryl; 3,3,3-trifluoro propyl, 3-chloropropyl or similar substituted alkyl etc.Component (C) can have line style, part branching, ring-type or netted molecular structure.Can be with two kinds or more kinds of molecular structure combinations.
Viscosity for organic hydrogen polysiloxanes has no particular limits.Preferably, the viscosity under 25 ℃ is in the scope of 3～10000 centipoises.Suggestion adds compsn with organic hydrogen polysiloxanes with such amount; Make with the mole number of silicon bonded hydrogen atom and heat-curable silicone rubber compositions of the present invention in the ratio of that contain and the mole number silicon bonded alkenyl in the scope of (0.5: 1)～(20: 1), preferred (1: 1)～(3: 1).If be lower than 0.5 with the ratio with the mole number silicon bonded alkenyl that contain in the mole number of silicon bonded hydrogen atom and the said composition, be difficult to compsn is cured to sufficient degree.On the other hand, if aforementioned proportion surpasses 20, this will form the bubble in the cured product.
Not with the limit of the object of the invention contradiction in, can be with heat-curable silicone rubber compositions and the various combinations of substances that generally are added in the conventional Zylox, for example zeyssatite, quartz powder, lime carbonate or similarly compatibilization filler; Titanium oxide, carbon black, red iron oxide or similar pigment; Triple Pressed Stearic Acid, Zinic stearas, calcium stearate, or the similar metal-salt of soap, above-claimed cpd, or similar releasing agent; With the hydrosilylation reactions retarding agent.
Prepare heat-curable silicone rubber compositions of the present invention through mixing said ingredients (A) equably to (D).According to preferable methods, at first, through in component (A) under the heating condition under 80～250 ℃ of temperature equably blending ingredients (B) prepare Zylox basis compsn, then, after cooling, base composition is mixed with component (C) with (D).Can be with hexamethyldisilazane or with the surface of hydroxyl with the lower molecular weight diorganopolysiloxanecompositions process element (B) of molecule two ends sealed.Can use surface treatment component and can be with component (B) and component (A) when mixing or carry out this processing before with the amount of 1～30 quality % with respect to the quality of component (B).The use of component (D) stops the partly solidified of Zylox basis compsn, even when under relatively-high temperature, mixing.Therefore when Zylox basis compsn is cooled off under 120～160 ℃ temperature, carry out the mixing of component (D) and can from mixing tank, remove said composition in identical TR.Therefore, through using component (D) to make the treatment time that the shortens said composition possibility that becomes.
Embodiment
To further describe the present invention in more detail with reference to embodiment, yet, should embodiment be construed as limiting the invention the scope of application.In these embodiment, all umbers all provide with mass parts, and viscosity is measured down at 25 ℃, utilize GPC (GPC) mensuration and reference PS to recomputate the value of number-average molecular weight.
[reference example 1]<no. 1 Zylox basis preparation of compositions; , following component mediates No. 1 Zylox basis of preparation compsn in the mixing tank through being packed into; In mediating mixing tank, mediated 60 minutes down with these component uniform mixing and at 175 ℃: 100 parts of molecule two ends are with the ethylene methacrylic radical siloxane of dimethylvinylsilyl-terminated and the rubber multipolymer (number-average molecular weight is about 350000) of dimethyl siloxane, and it is made up of 99.8 moles of % dimethyl siloxane units and 0.13 mole of % methyl vinyl siloxane unit; 40 parts have 300mm
2The dry method fine silica end of the BET specific surface area of/g; Use the softening agent of the viscosity of the end capped dimethyl siloxane oligopolymer of silanol form with 10 parts of molecule two ends as 30mPas.
[reference example 2] < No. 2 Zylox basis preparation of compositions>is through No. 2, following component uniform mixing in mediating mixing machine preparing Zylox basis compsn: 100 parts of molecule two ends are with the ethylene methacrylic radical siloxane of dimethylvinylsilyl-terminated and the rubber multipolymer of dimethyl siloxane (number-average molecular weight is about 350000), and it is made up of 99.8 moles of % dimethyl siloxane units and 0.13 mole of % methyl vinyl siloxane unit; 45 parts of wet-process fine silica ends; Use the softening agent of the viscosity of the end capped dimethyl siloxane oligopolymer of silanol form with 5 parts of molecule two ends as 30mPas.Then, this mixture was further mediated 60 minutes down at 175 ℃.
[embodiment 1～3; Comparative example 1 and 2] in double roll mill, prepare uniform mixture by 100 parts of No. 1 Zylox basis compsn and 1.5 parts of cerium oxide that are shown in the following table 1 that in reference example 1, obtain.The stability in storage of the mixture that test obtains.Also in double roll mill through cerium oxide listed in No. 1 Zylox basis compsn that 100 parts are obtained in reference example 1 and the 0.1 part of table 1 and with 0.4 part 2,5-dimethyl--2,5-two (t-butyl peroxy) hexane mix and prepare uniform mixture.With the heat-curable silicone rubber compositions heating and the curing that obtain.The product that obtains is used for manufacturing to be used to measure compressive set and to be used to test stable on heating sample.Sample through use obtains is measured compressive set and thermotolerance, and the result that will measure and test is shown in the following table 2.
[embodiment 4～6; Comparative example 3] mix with the cerium oxide shown in 0.05 quality % or the 0.01 quality % following table 3 through No. 1 Zylox basis compsn that will in reference example 1, obtain and to prepare uniform mixture.Then, with 100 parts of mixtures that obtain in double roll mill with 0.4 part 2,5-dimethyl--2,5-two (t-butyl peroxy) hexane uniform mixing.The compsn of preparation is heated and solidifies, and the product that obtains is used for making the sample that is used to measure compressive set, compare the content of ceria oxide powder and the relation between the compressive set then.Prepare the Zylox sheet material of 2 mm thick through the above-mentioned heat-curable silicone rubber compositions that contains the ceria oxide powder of 0.05 quality % of thermofixation, and detect the transparency of the sheet material that obtains.The result is shown in the following table 3.
[embodiment 7; Comparative example 4 and 5] through in double roll mill with 100 parts of No. 2 Zylox basis compsns that in reference example 2, obtain and cerium oxide of measuring shown in the following table 4 and with 0.4 part 2; 5-dimethyl--2,5-two (t-butyl peroxy) hexane mixes and prepares uniform mixture.With the heating of the product that obtains and solidify, and cured product is used for making is used to measure stable on heating sample.Stable on heating mensuration result is shown in Table 4.
Table 1
| BET specific surface area (m 2/ g) | Median size (nm) | Total light transmittance (%) | Primary particle diameter (nm) | Percent crystallinity (%) | Purity (%) | |
| Ceria oxide powder A | 115 | 85 | 90 | 7 | 36 | 70 |
| Ceria oxide powder B | 115 | 34 | 93 | 7 | 36 | 70 |
| Ceria oxide powder C | 55 | 959 | 90 | 15 | 63 | 99.8 |
| Ceria oxide powder D | 135 | 3268 | 87 | 6 | 46 | 99.9 |
| Ceria oxide powder E | 8 | 662 | 85 | 110 | 85 | 99.9 |
Use the characteristic of the ceria oxide powder shown in the following method mensuration table 1.Ceria oxide powder A: ceria oxide powder (the TakiKagaku Co. that obtains by cerium salt solution through sol-gel method; Ltd. product, trade mark: Niedral U-100): through sol-gel method by cerium salt solution preparation and with the surface-treated ceria oxide powder of AS.Ceria oxide powder B:Taki Kagaku Co., the product of Ltd., trade mark: Niedral W-100): obtain by cerium salt solution and with phosphoric acid and the surface-treated ceria oxide powder of cats product through sol-gel method.Ceria oxide powder C: (C.I.Kasei Co., the product of Ltd., trade mark: Nanotek CeO
2): the ceria oxide powder that obtains by the gas phase thermolysis.Ceria oxide powder D: through dioxide gas being blown into ceria oxide powder (Nikki Co., the product of Ltd.; Trade mark: the ceria oxide powder of the 3 quality % aqueous dispersions that Kojundo Sanka Cerium (High-Purity Cerium Oxide)) obtain in (it obtains through mechanical disintegration behind the roasting cerium carbonate powder) with pH3.8.Ceria oxide powder E: the ceria oxide powder (Rhodia Japan Co., the product of Ltd.) that obtains through the gas phase thermolysis.
< primary particle diameter>is converted into spherical basically this value that obtains through true density and the BET specific surface area by cerium oxide.< percent crystallinity>will use the integrated intensity of the determination data that Shimadzu X-ray diffractometer XRD-7000 and Shimadzu X-ray diffractometer XRS-6100 percent crystallinity software obtains to be divided into percent crystallinity component and amorphous component, based on a component ratio of another component confirmed percent crystallinity then.< median size>is through using the particle determining instrument (product of Particle Sizing Systems Co.; Model.NICOMP Model 370) and size distribution determining instrument (Nikkiso Company, the product of Ltd.; MICROTRAC HRA MOLDEL 9320-X100) dynamic scattering method is measured median size.< purity>is measured purity through x-ray fluorescence analysis.< total light transmittance>will contain 99.8 moles of % dimethyl siloxane units and 0.13 mole of % methyl vinyl siloxane unit with dimethyl-vinyl silyl with the ethylene methacrylic radical siloxane of molecule two ends sealed and the rubber multipolymer of dimethyl siloxane (number-average molecular weight: 350000) with 0.1 quality % ceria oxide powder uniform mixing and mediating in double roll mill.With the mixture that obtains of 100 deals and 0.4 part 2,5-dimethyl--2,5-two (t-butyl peroxy) hexane mixes, and through 170 ℃ of lower compression mouldings 10 minutes mixture being formed the thick cured sheet of 1mm.By Nippon Denshoku Industries Co., the WaterAnalyzer-200N of Ltd. measures the total light transmittance through the sheet material that obtains according to JIS K7105.Air is used as reference.
Table 2
Table 3
Table 4
The storage stability test of compsn < Zylox basis>with No. 1 Zylox basis compsn of preparation in the 200g reference example 1 and the ceria oxide powder uniform mixing in double roll mill in the 3g table 1, and mixture is packed into and is sealed in the circular metal container with 1 liter of capacity.Subsequently, this container was kept three days in being set in the heated oven of 70 ℃ of temperature or 100 ℃.When heating is accomplished, with the Zylox basis compsn that obtains under the following condition in 6 " mediated 3 minutes in the double roll mill: roller spacing: 3mm; Rotational frequency: 20rpm and 28rpm.When accomplishing mixing and kneading, rubber composition is peeled off with sheet-form from roller.The slipperiness of sheet material is carried out visually inspect and according to following standard evaluation: zero: smooth surface *: the surface is for wavy and coarse, and rubber composition becomes sticky and partly gelling.< compressive set>prepared the compressive set test sample through making heat-curable silicone rubber compositions in 10 minutes at 170 ℃ of following pressure mouldings.Then sample is put into the heated oven that is adjusted to 200 ℃ and made its regelate in 4 hours through heating.The sample that obtains is measured compressive set in 180 ℃ of lower compression, 25% experience 22 hours and according to JIS K6262.< thermal test of Zylox>is through preparing the Zylox sheet material of 2 mm thick in 10 minutes at 170 ℃ of lower compression moulding heat-curable silicone rubber compositions.Then this sheet material is put into the heated oven that is adjusted to 200 ℃ and carried out regelate in 4 hours through heating.Utilize A type hardness tester meter according to the hardness that JIS K6253 measures the sheet material of handling, measure tensile strength and elongation according to the regulation of JISK6251.Through further sheet material aging of the above-mentioned manufacturing of test of heating in being adjusted to the heated oven of 230 ℃ or 250 ℃ 96 hours.To sheet material tested for hardness, tensile strength and elongation once more by the heating test.Following calculating is pressed in the maintenance of changes in hardness, tensile strength and the maintenance of elongation: the maintenance (%) of the maintenance (%) of-changes in hardness=(hardness after wearing out)-(hardness before aging)-tensile strength=(tensile strength after aging/preceding tensile strength wears out) * 100-elongation=(elongation after aging/aging preceding elongation) * 100
The feasible moulding silicone rubber products that shows excellent thermotolerance, low compression deformation and be exposed to above the low deterioration behind 200 ℃ the high temperature that forms of heat-curable silicone rubber compositions of the present invention becomes possibility.Therefore, the manufacturing of the rubber components that above compsn is suitable under hot conditions, operating, you are like the fixing roller of near the rubber components of motor car engine, working, electro-photography apparatus, pressure roll etc.Have the excellent transparency or translucency when in addition, the feasible formation of heat-curable silicone rubber compositions of the present invention has high heat resistance, have low compression deformation and have the silicone rubber products that is exposed to above hanging down the physicals loss behind 200 ℃ the high temperature and become possibility.In view of foregoing, said composition is suitable for making for example lampshade etc. of the parts that must have the transparency and under hot conditions, work.
Claims (5)
1. heat-curable silicone rubber compositions; Its amount with 0.001～10 quality % contains surface treated ceria oxide powder through the sol-gel method preparation; And be characterised in that when when layer of light through the thick dimethyl polysiloxane rubber that contains alkenyl of 1mm; Wherein the said ceria oxide powder of 0.1 quality % is scattered in this rubber, is equal to or greater than 90% according to the total light transmittance of JIS K7105.
2. according to the heat-curable silicone rubber compositions of claim 1, wherein this ceria oxide powder is carried out surface treatment with the ammonia salt of tensio-active agent, ortho-phosphoric acid, ortho-phosphoric ammonia salt, ortho-phosphoric an alkali metal salt, condensed phosphoric acid, condensed phosphoric acid or an alkali metal salt of condensed phosphoric acid.
3. according to the heat-curable silicone rubber compositions of claim 1, wherein the mean diameter of this ceria oxide powder is 10～200nm, and this mean diameter is confirmed by the dynamic scattering method of using particle determining instrument and size distribution determining instrument.
4. heat-curable silicone rubber compositions, it comprises: 100 mass parts contain the diorganopolysiloxanecompositions (A) of alkenyl; 5～150 mass parts reinforcing fillers (B); Solidifying agent (C) is to be enough to solidify the amount of aforementioned heat-curable silicone rubber compositions; And ceria oxide powder (D); When its amount with 0.1 quality % is distributed in the dimethyl polysiloxane rubber that contains alkenyl; When light passes through the layer of the thick said dimethyl polysiloxane rubber of 1mm; 90% the total light transmittance of being equal to or greater than according to JIS K7105 is provided, and the content of component (D) in said composition is 0.001～10 quality %, and this ceria oxide powder is the surface treated ceria oxide powder through the sol-gel method preparation.
5. ask 4 heat-curable silicone rubber compositions according to claim, wherein this component (C) is an organo-peroxide.
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| JP356606/2006 | 2006-12-28 | ||
| JP2006356606 | 2006-12-28 | ||
| PCT/JP2007/075418 WO2008082001A1 (en) | 2006-12-28 | 2007-12-27 | Thermosetting silicone rubber composition |
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| US (1) | US8084529B2 (en) |
| EP (1) | EP2105467B1 (en) |
| JP (1) | JP5410762B2 (en) |
| KR (1) | KR101455123B1 (en) |
| CN (1) | CN101679747B (en) |
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| CN101775219B (en) * | 2010-01-12 | 2012-06-27 | 山东大学 | Radiation-resistant addition type room temperature vulcanized liquid silicone rubber and preparation method thereof |
| JPWO2011135780A1 (en) * | 2010-04-27 | 2013-07-18 | 信越化学工業株式会社 | Light emitting device and manufacturing method thereof |
| JP5803652B2 (en) * | 2010-12-28 | 2015-11-04 | 信越化学工業株式会社 | Method for producing optical sheet for concentrating solar cell |
| WO2013084699A1 (en) | 2011-12-08 | 2013-06-13 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Hydrosilylation-curable silicone rubber composition |
| JP5174270B1 (en) | 2012-08-02 | 2013-04-03 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermosetting silicone rubber composition |
| CN105612219B (en) * | 2013-09-03 | 2018-12-14 | 道康宁东丽株式会社 | Silicone gel composition and application thereof |
| US10502995B2 (en) * | 2014-06-19 | 2019-12-10 | Inkron Oy | Dielectric siloxane particle films, and devices having the same |
| JP6524901B2 (en) | 2015-12-08 | 2019-06-05 | 信越化学工業株式会社 | Silicone rubber composition and cured product thereof |
| JP6583160B2 (en) * | 2016-06-24 | 2019-10-02 | 信越化学工業株式会社 | Silicone rubber composition and silicone rubber |
| JP6702233B2 (en) | 2017-03-09 | 2020-05-27 | 信越化学工業株式会社 | Addition-curable organopolysiloxane resin composition, cured product of the composition, and semiconductor device having the cured product |
| JP6738776B2 (en) * | 2017-08-01 | 2020-08-12 | 信越化学工業株式会社 | Silicone rubber composition |
| JP7401874B2 (en) | 2020-03-31 | 2023-12-20 | 横河電機株式会社 | Estimation system, estimation device and estimation method |
| CN116235257A (en) | 2020-07-29 | 2023-06-06 | 埃肯有机硅法国简易股份公司 | Crosslinkable silicone elastomer composition comprising heat-resistant additive |
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| JPWO2008082001A1 (en) | 2010-04-30 |
| EP2105467B1 (en) | 2012-02-22 |
| EP2105467A1 (en) | 2009-09-30 |
| US8084529B2 (en) | 2011-12-27 |
| ATE546490T1 (en) | 2012-03-15 |
| CN101679747A (en) | 2010-03-24 |
| EP2105467A4 (en) | 2010-11-03 |
| KR101455123B1 (en) | 2014-10-27 |
| KR20090111318A (en) | 2009-10-26 |
| WO2008082001A1 (en) | 2008-07-10 |
| JP5410762B2 (en) | 2014-02-05 |
| US20100280163A1 (en) | 2010-11-04 |
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